Products obtainable from 4,6-diamino-1.3-xylene and process of making.



stances UNITED STATES PATENT OFFICE.

MARSTON TAYLGR BOGEBT, OF NEW YORK, N. Y.

PRODUCTS OBTAINAB LE FBOM 4.6-DIAMINO-L3-XYLENE AND PROCESS OF MAKING.

No Drawing.

To all' whom it may concern:

Be it known that I, MARSTON TAYLOR Boonn'r, a citizen of the UnitedStates, and a resident of the cit of New York, borough of Manhattan, intli New York, have invented certain newand useful Improvements inProducts Obtainable from 4.6-Diamino-L3-Xylene and Processes of Making,of which the following is such a full, clear, and accurate descriptionas will enable any one skilled in the art to which .it 'appertains tomake and usev the same.

My invention relates to the production of certain new mother-substancesand the production therefrom of a series of new and useful products.Both the mother-suband the products therefrom, although differingconsiderably in properties, possess in common the following genericnucleus One seriesof these products containsthe following specificnucleus Specification of Letters Patent.

e county and State of.

Patented July 16, 1912.

Application fled April 22, 1909. Serial No. 491,499.

and which is hereinafter referred to as the naphthotetrazin nucleus, orthe 1, 3, .7, 9 naphthotetrazin nucleus.

By acetylating and then oxidizing 4.6- diamino-L3-xylene, I obtain thenew body 4.6diacetamino-1.3-phthalic acid according to the followingequation:

By boiling the latter substance-with excess of hydrochloric acid, Iobtain the hydroclilorid of 4.(i-diamino-lfi phthalic acid, according tothe following equation By dissolving the latter substance in causticsoda solution and acidifying with acetic acid, I obtain the new4.6-diamino-L3- phthalic acid, according to the following equations Byboiling the LG-diacetamino-lfiphthalic acid with excess of acetica'nhydrid and concentrating the solution, I' obtain crystals ofanothennew body, a bis-aceta1ithranil, according to the followingequation:"

By condensing the latter substance with a primary monamin, I obtainanother'new CH;CO.N\/\/N.COCH:

in which R is hydrogen or a simple or substituted alphyl or arylradical. Or, by condensing the aboye bis-acetanthranil w th an in whichAr is a simple or substituted aromatio' nucleus. 4

' By diazotizing the latter compounds in the well-known way andcombining with ons ncanmncoonmwcnscoorn suitable couplers, I produce newseries of useful azo dyestuffs, all of which are characterized bycontaining the following nucleus oH3-o c-L:H N:N-Ar-I'\' in which Ar isa simple or substituted aromatic nucleus.

From the 4.6-diacetamino-1.3-phthalic acid, I believe that other groupsof dyes, as well as compounds valuable in the treatment of disease andin other ways, niay be obtained, containing in common with the said azodyestuffs the said generic nucleus n n o 0 The compounds produced bycondensing the said bis-acetanthranil with prlmary monamins or witharomatlc.primary diamlns, as well as the dyestuffs obtained from thesecondensation products, all contaln the following nucleus Example 1: 209parts of the hydrochloridof 4.641iamino-LS-xylene are mixed with 104parts of fused sodium acetate; about parts acetic anhydrid are thenadded and the mixture boiled for an hour. -When cold, the mixture ispoured into 1000 parts of warm water and the whole boiled down to halfits original bulk and then'allowed to cool. The crystals oftfi-diacetamino-lfixylene which separate are filtered out, washedthoroughly with water and dried.

Recrystallized from glacial acetic acid, the

compound is obtained in the form of colorless needles, melting at about295 C. (con) This is the pure 4.6-diaceta1n1no-1.3-xylene. It is not anew substance, but has been described before in chemical literature.From this point on, all the compounds described are, I believe, entirelynew. One part of this 4.6-diaeetamino-L3-xylcne and two parts magnesiumsulfate are added to 100 parts of water. The mixture is heated toboiling and three parts of finely pulverized potassium permanganate areadded gradually to the boiling solution. \Vhen the oxi dation iscompleted, the hot solution. is fil- "chloric acid and the mixtureheated to boiling. After boiling for about ten or fifteen minutes, aclear solution is obtained and almost immediately pale yellowish needlesof the hydrochlorid of 4.6-diamino-1.3-phthalic acid begin to separate.The boiling is continued for five minutes longer, the solution allowedto cool, the separated crystals are filtered out, washed withconcentrated hydrochloric acid and dried. The crystals thus obtainedconsist of the hydrochlorid of h'fi-diamino-1.3-phthalic acid inpractically pure condition, and melt at about 229230 C. (0012) One partof this hydrochlorid is suspended in about ten parts of water anddissolved by adding caustic soda to faintly alkaline reaction. ()nacidifying this solution with acetic acid, the free 4.(Sdiamino-1.3-phthalic acid separates as a colorless amorphous precipitate. Theprecipitated acid is filtered out and may be further purified bydissolving it in dilute caustic soda solution and re-precipitating withacetic acid. \Vhen pure, it forms a colorless powder, gradually turningpink on standing, and melts at about 235 C. (coin) with decomposition.It is very slightly soluble in water, alcohol, benzole, ether,chloroform or amyl acetate. Boiled with excess ofacetic anhydrid, itpasses first into the 4.6-diacet an'iino-LS-phthalic acid and then intothe bis-acetanthranil hereinafter described. I have also produced manyderivatives of the above LG-diacetaiiiino-l.3-phthalic acid and of theLG-diamino-l.3-phthalic acid as, for example, salts, esters, andderivatives in which the hy'drogens of the amino groups were replaced byother groups.

Example 2: ()nepart of 4.6diaceta1nino- 1.3-phthalic acid is boiled withfour parts of acetic anhydrid for half an hour or an hour. On cooling toroom temperature, long, colorless, fine needles of the bis-acetanthranilseparate. These crystals are filtered out, washed with acetic anhydrid,then with gasolene, and dried. As thus obtained, the bis-acetanthranilis pure and melts at about 282.3 0. (con) Boiled with water, it isgradually re-converted to the 4.6diacetamino-1.3-'phthalic acid again.

Example 3: One part of the above bisacetanthranil is boiled for aboutfifteen minutes with an equal part by weight of anilin.

x ZN /\Tu i CgHr -N N-C5Hs ,In lieu 'of theanilin above referred to, l

have 'used successfully ammonia, methylamin, normal propylamin, betanaphthylamin, hydrazin and phenylhydrazin, and obtained condensationproducts of similar ty e. believe that other bis-acylanthrani s andother rimary amins than those mentioned can a so be used.

Example 4; Onepart of the above bisacet-anthranil is heated with twoparts of diorthoanisidin for five or ten minutes at 168- 172 C. Whencold, the mass is pulverized fine, washed thoroughly with dilute causticsodasolution, dissolved in dilute hydrochloric acid, filtered, thefiltrate made Lightly alkaline by the addition of caustic a, theprecipitate filtered out, washed thoroughly with water and dried. It isthen generally sufiiciently pure for the prep aration of azo dyestuti's.If desired, it can be further purified by re-dissolving it. in dilutehydrochloric acid and rc-precipitating with caustic soda. When washedand dried, it forms a dark powder, melting at about 122 C. (cor.),readily soluble in 95}, alcohol or in dilute hydrochloric acid, veryslightly soluble in water orin dilute aqueous solutions of the causticalkalics. This is one of my mother-substances for the production of azodyestutl's, and I believe that it has the following constitutionalformula In lieu of the di-orthoanisidin above referred to, I havesuccessfully employed the following di-primary aromaticdiaminszmetaphenylene diamin, paraphenylene diamin, metatolyene; diamin,me-taxylylene diamin, benzidin, tolidin, and ethoxybenzidin. I believethat other aromatic .di-prilnary diaminsand other bis-acylanthranilsthan those above mentioned may also be used.

. large number of these new dyes.

experiments indicate that condensation products of the above type havethe followng clniracteristics:-They contain two or more diazotizablcprimary amino groups. They are in most cases pulverulent solids, ofdefinite meltingor decomposing-points; very slightly soluble in water orin dilute aqueous caustic soda solution, soluble in dilute hydrochloricor sulfuric acid, and more or less readily soluble in 95% alcohol.I)is-.

solved in concentrated hydrochloric acid and treated with stannouschlorid, they sutier reduction. Most of them are strongly triboelectric.Diazotized in the well-known way, they yield tetrazo bodies which unitewith suitable couplers to form valuable azo dyestuffs, and in this way Ihave produced a Heated with phthalic anhydrid, inpresencc of zincc-hlorid, they condense to new dyes of quinolin yellow type. All ofthese condensation products are further characterized by containing thefollowing nucleus in which Ar is a simple. or substituted aromaticnucleus.

The condensation products obtained by the above process vary inproperties according to the particular l1is-acylanthranil and diaminused. Thus, for example, the condensation products obtained frombis-acetanthranil and various diamins show the following properties:from inetaphenylene diamin, the condensation product obtained is in theform of a nearly colorless powder, which softens at about 255 (1. andmelt-s atabout 2(3526t3 (1. (con); from paraphenylcne diamin, thecondensation product. obtained is in the form of a dark gray powder,which melts with blackening at about.- 260261 G. (cor.); from2.4--diamino tolu one, the condensation product obtained is in the formof a nearly colorless powder, melting at about 255-256" C. (con); from4.6-diamino-l.3-Xylene, the condensation product is in the form oi? ayellowish powder, melting, at about 27527(' OJ (cola); from benzidin,the condensation product obtained. is in "the torn: of a slate-coloredpowder, which remains unmelted at 325 C. (c012); from orthotolidin, thecondensa' form of a dark powder, melting at about Example 5: (396 partsof the condensation product obtained from the bis-acetanthranil anddi-orthoanisidin described in Example 4:) is dissolved in dilutehydrochloric acid so that the solution contains a total of 150 partshydrogen chlorid. tion is cooled to 0 (1. and diazotized by the additionof 138 parts sodium nitrite in aqueous solution. This tetrazo solutionis then stirred into a. stronglyv alkaline solution of (ii-l6 parts ofl.8iliaininciraphthalene- 4.6-disullo acid. The alkaline solution isslightly acidified with lrvdrochloric acid, then made slightly alkalineagain by the addition of caustic soda, and the dycstutf is precipitatedby the addition of sodium chlorid to the solution. It is a blue-blackpowder, soluble in water, and in acid bath dyes silk from violet to deepblue depending upon the amount of dyestuif used. This is one of my newazo dyestufi's. In lieu of the condensation product used in the aboveexample, I have successfully employed the other condensation productsdescribed in Example 4, and I believe that other compounds of similarstructure may also be employ ed. In lieu of theLS-diaminonaphthalene-(I-fi-disulto acid used above as the coupler, Ihave successfully employed many other well-known couplers (chieflyaromatic amins, phenols, and their sulfonic and carboxylic acids), and Ibelieve that most of the couplers generally used in the preparation ofazo dyestuti'scan also be used successfully with my newtetrazo bodiesfor the production of new azo dyestuffs.

Instead of using the above condensation products from bis-acetanthraniland an arcmatic di-primary diamin as primary components in theproduction of azo dyestuffs, I have also used them as secondarycomponents or couplers to combine with various well-known diazo andtetrazo bodies and in this way have produced other new azo dyes. ()fthese new aZo dyestuffs, those of pa raminoazo structure may be againdiazotized and coupled, and I have in this way obtained other newdyestuffs of polyazo character. My experimentsindicate that all of theseazo dycstuli's are substantive for silk and wool. Some are substantivefor cotton. They include acid, basic, and mordantdyes, and can beapplied to the fiber in substantially the same manner as other acid,basic, and mordant azo dyestuffs. They may be applied to the fiber asfinished dyes, or the diazotizing and coupling may be carried out withinthe fiber itself, thus producing what are known as developed dyes,ingrain colors, &c. As a class, these new azo dyestuffs arecharacterized by the beauty and peculiarity of the shades they produce;by their fastness to light, to alkali, to acid, to washing and milling.and to bleaching. They penetrate the fiber thoroughly and equalize well.All are more or less readily soluble in water. I understand that theseThe solunew azo dyestuffs differ from all others in containing thefollowing nucleus:

in which Ar is a simple or substituted aromatic nucleus.

My experiments indicate that these new azo dyestuffs show the followingproperties ':-'lheir solutions in concentrated hydrochloric acid arerapidly reduced and decolorizcd by the addition of stannous chlorid, theaxe groups being split between the two nitrogcus. It the naphthotetrazincomp0- ncnt be separated from this reduced solution, re-diazotized andcombined with the same component or components used in the production ofthe original dyestutl, an azo dyestutt different from the original oneresults; in other words, these new azo dye stalls contain double bondsand CO groups, either or both of which may undergo some reduction duringthe treatment and 4 e 11aphthotetrazin component separated from thereduced solution is not the same as the one started with. They dissolvein concentrated sulfuric acid to richly colored solutions, the colorvarying with the dyestuti used, On diluting these solutions with Water,the color base generally separates in flocculcnt form. They can becondensed with phthalie anhydrid, in presence of zinc rhlorirhto newdyes of quinolin yellow type.

In the following table the shades of some of the new dyestuffs obtainedfrom bis-acetanthranil are given. The first column gives the diamin withwhiehthe bis-acetanthranil was condensed to form the mother-substance,the second the coupler used with the diazotized mother-substance, andthe third the color on s1lk:

i. Metaphenyb l-naphthol-tsulfoacid Bright red one diamin. 2. Do1,S-rlipxynaphthalene-3.7-disulfo Rose red.

K 3. Do 1.8-r1iaminonaphthalenc4.6-di- Purp1e..

sull'o acid. 4. Do 8-am i1no-1-naphtliol-3.6-disulfo Purple.

RC1 5. Paraphenyl- 1'naphthylamine-fi-sulto aeid Brown.

ene diamin. 6 l)o..;.. l-naphtholl-sulfo acid Light eatawba. 7. Benzidinl-naphtholi-sulio acid Rose red. 8. D0 1.5-dioxynaphthalene-3.7-disu1toDark pink.

acid. 9. Do 1.841iamin0nuphthaleneA.(i-di- Purple.

sulfo acid. 10. Do 8amino-1-naphthol 3.6-disulfo Purple.

acid. 11. To1idin.. Salieylieacid otlzhro ye1- ow. 12. Do Resoreinol...L i g h is brown. 13. Di-orthoani- Lnaphthol-d-sull'o aeid-.. Darkviolet.

idin. Lt. Do Lfi-dipxynaphthalcnefl.7- lisuHo Red purple.

. acu. 15. Do 1.X-diaminonaphthalene-4.6-rli- Darkblue. sullo ac Y .16.Do S-amino-l-naph11101-3.(i-disl1lio l)a.rkhluc.-

acid. 17. Ethoxyben- 2naphthylamine-S-sull'oacid Oraugered.

zidin.

Do Znaphthol-iiJ-disufivacid Heliotro e.

Having thus described my invention,what I claim is: p

1. The process of producing new Substanoes containing the nucleus:

3. As an article of manufacture, a Substance which can be obtained froma bisacylanthranil and which contains the nucleus:-

4. As a new product, a substance which can be obtained by condensing abis-a'cetanthranil with a primary amin, and whose constitutional formulacorresponds to the following in which R is a carbon containing group.

It is hereby certified that 1912 upon the application ofMarstonimprovement in Products esses of Making, an error appears in theprinted specification requiring last symbol in line for CH read 0H,; and

as follows: Page 2, line 5, formula,

that the said Letters Patent should be read with this correction thereinthat the a sub- 5. Asa new product, a substance which can be obtained bycondensing a bis-acetanthranil with an aromatic rimary diamin, and whoseconstitutional ormula contains the following -A.r-N

in which Ar. is an aromatic residue.

6. As a new product, an azo dyestufi' which can be produced from a.condensation product of a bis-acetanthranil and an aromatic di-primarydiamin', and which contains the following nucleus 2- cu e c-cm'-N;N-'-'Ar-N K/ ri-Ar-N=N- 8 t in which Ar. is an aromatic residue, andwhose solution in concentrated hydrochloric acid is reducedandde-colorized by the addition of stannous chlorid, the azo groupsbeing split between the two nitrogens and one product of this splittingbeing a diamino derivative of a reduced 1, 3, 7, 9- naphthotetrazinnucleus which, when diazotized and coupled with the other component .orcomponents used in the preparation of the orlginal'dyestuif, gives anazo dyestuff diflerent from the orlglnal one.

In testimony whereof, I have hereunto signed my name in the presence oftwo subscribing witnesses.

MARSTON TAYLOR BOGERT.

Witnesses:

FRANK E. ROFFMAN, W. A. PAULING.

in Letters Patent No. 1,032,734, granted July 16, Taylor Bogert, of NewYork, N. Y., for an Obtainable from l.6Diamino-L3-Xylene andProccorrection same may conform to the record of the case in the PatentOffice.

\ i Signed and sealed this 17th day of September, A. D., 1912.

[SEAL] o. c. BILLINGS,

Acting Commissioner of Patents.

Having thus described my invention,what I claim is: p

1. The process of producing new Substanoes containing the nucleus:

3. As an article of manufacture, a Substance which can be obtained froma bisacylanthranil and which contains the nucleus:-

4. As a new product, a substance which can be obtained by condensing abis-a'cetanthranil with a primary amin, and whose constitutional formulacorresponds to the following in which R is a carbon containing group.

It is hereby certified that 1912 upon the application ofMarstonimprovement in Products esses of Making, an error appears in theprinted specification requiring last symbol in line for CH read 0H,; and

as follows: Page 2, line 5, formula,

that the said Letters Patent should be read with this correction thereinthat the a sub- 5. Asa new product, a substance which can be obtained bycondensing a bis-acetanthranil with an aromatic rimary diamin, and whoseconstitutional ormula contains the following -A.r-N

in which Ar. is an aromatic residue.

6. As a new product, an azo dyestufi' which can be produced from a.condensation product of a bis-acetanthranil and an aromatic di-primarydiamin', and which contains the following nucleus 2- in which Ar. is anaromatic residue, and whose solution in concentrated hydrochloric acidis reduced andde-colorized by the addition of stannous chlorid, the azogroups being split between the two nitrogens and one product of thissplitting being a diamino derivative of a reduced 1, 3, 7, 9-naphthotetrazin nucleus which, when diazotized and coupled with theother component .or components used in the preparation of theorlginal'dyestuif, gives an azo dyestuff diflerent from the orlglnalone.

In testimony whereof, I have hereunto signed my name in the presence oftwo subscribing witnesses.

MARSTON TAYLOR BOGERT.

Witnesses:

FRANK E. ROFFMAN, W. A. PAULING.

in Letters Patent No. 1,032,734, granted July 16, Taylor Bogert, of NewYork, N. Y., for an Obtainable from l.6Diamino-L3-Xylene andProccorrection same may conform to the record of the case in the PatentOffice.

\ i Signed and sealed this 17th day of September, A. D., 1912.

[SEAL] o. c. BILLINGS,

Acting Commissioner of Patents.

